Kinetic hydrate inhibitors for controlling gas hydrate formation in wet gas systems

ABSTRACT

The present invention generally relates to methods and hydrate inhibitor compositions for inhibiting the formation of hydrates in a fluid comprising gas and water. More specifically, the method comprises contacting a hydrate inhibitor composition to a fluid. The hydrate inhibitor composition comprises a nonpolar solvent; a polar solvent; and a polymer, an oligomer, a dendrimer, or an acid or salt thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Non-Provisional patentapplication Ser. No. 15/441,656 filed on Feb. 24, 2017, which claims thebenefit of U.S. Provisional Patent Application Ser. No. 62/300,552 filedon Feb. 26, 2016, the disclosure of which is incorporated herein byreference in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

THE NAMES OF PARTIES TO A JOINT RESEARCH AGREEMENT

Not applicable.

REFERENCE TO A SEQUENCE LISTING, TABLE, OR COMPUTER PROGRAM LISTINGAPPENDIX SUBMITTED ON A COMPACT DISC AND AN INCORPORATION-BY-REFERENCEOF THE MATERIAL ON A COMPACT DISC

Not applicable.

FIELD OF THE INVENTION

The present invention generally relates to a method for inhibitinghydrate formation in a fluid comprising water and a gas. The methodcomprises contacting an effective amount of a hydrate inhibitorcomposition comprising a nonpolar solvent, a polar solvent, and either apolymer, an oligomer, a dendrimer, or an acid or salt thereof, to afluid.

BACKGROUND OF THE INVENTION

Natural gas hydrates are crystalline solids composed of water and gas.In these solids, the gas molecules (guests) are trapped in watercavities (host) that are composed of hydrogen-bonded water molecules.Methane is the main gas in naturally occurring gas hydrates, howevercarbon dioxide, hydrogen sulfide, and less frequently, otherhydrocarbons such as ethane and propane can be found within the hydratestructure. In 1934, Hammerschmidt determined that natural gas hydrateswere blocking gas transmission lines, frequently at temperatures abovethe ice point. This discovery caused a more pragmatic interest in gashydrates and led to the regulation of the water content in natural gaspipelines.

Gas hydrates can be easily formed during the transportation of oil andgas in pipelines under certain conditions. Factors affecting gas hydrateformation include gas composition, water content, temperature, andpressure, particularly low temperature and high pressure. While thesecrystalline cage-like structures are initially small, they are able toagglomerate into solid masses called gas hydrate plugs. The formation ofgas hydrates within a pipeline often results in lost oil or gasproduction, damage to transmission lines and equipment, and safetyhazard to field workers.

Three types of hydrate inhibitors are currently available to the energyindustry for controlling gas hydrates: thermodynamic hydrate inhibitors(THIs), kinetic hydrate inhibitors (KHIs), and anti-agglomerants (AAs).Kinetic hydrate inhibitors are substances that can delay gas hydratenucleation and crystal growth at a given temperature and pressure.Water-soluble polymers combined with small organic molecules arecommonly used as kinetic hydrate inhibitors. The polymers must containfunctional group(s) capable of hydrogen bonding to water molecules orgas hydrate particle surfaces and hydrophobic group(s) adjacent to orthe hydrogen bonding groups.

Accordingly, there is an ongoing need for compositions and methods thateffectively prevent hydrate formations in water and gas transportationand handing processes, particularly those formulations without an oilphase which results in a water cut approaching 100%.

BRIEF SUMMARY OF THE INVENTION

One aspect of the invention is directed to a method for inhibitinghydrate formation in a fluid comprising water and a gas (i.e.,hydrocarbon gas). The method comprises contacting the fluid with aneffective amount of a hydrate inhibitor composition. The hydrateinhibitor composition comprises a nonpolar solvent, a polar solvent, andeither a polymer, an oligomer, a dendrimer, or a combination thereof.

Another aspect of the invention is directed to a method for inhibitinghydrate formation in a fluid comprising water and a gas, the methodcomprising contacting the fluid with an effective amount of a hydrateinhibitor composition. The composition comprises from about 5 wt. % toabout 55 wt. % of heavy aromatic naphtha, and from about 0.1 wt. % toabout 15 wt. % of 2-ethyl hexanol, and from about 0.1 wt. % to about 50wt. % of a kinetic hydrate inhibiting polymer or a kinetic hydrateinhibiting oligomer.

An additional aspect of the invention is directed to a method forinhibiting hydrate formation in a fluid comprising water and a gas(i.e., hydrocarbon gas). The method comprises contacting the fluid withan effective amount of a hydrate inhibitor composition. The hydrateinhibitor composition comprises an oil-soluble corrosion inhibitor andeither a polymer, an oligomer, a dendrimer, or a combination thereof.

Another aspect of the invention is directed to a method for inhibitinghydrate formation in a fluid comprising water and a gas, the methodcomprising contacting the fluid with an effective amount of a hydrateinhibitor composition. The composition comprises from about 5 wt. % toabout 55 wt. % oil-soluble corrosion inhibitor and from about 0.1 wt. %to about 55 wt. % of a kinetic hydrate inhibiting polymer or a kinetichydrate inhibiting oligomer.

Other objects and features will be in part apparent and in part pointedout hereinafter.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

Not applicable.

DETAILED DESCRIPTION OF THE INVENTION

Hydrate inhibitor compositions are provided with improved performance inproduction streams having a high water cut. In particular, these hydrateinhibitor compositions are well suited for wet gas systems. Thesestreams pose a challenge to control gas hydrate formation because of thehigh water-cut as the efficacy of the hydrate inhibitor is sometimesreduced in the absence of an oil phase. The hydrate inhibitorcompositions provided herein can be formulated with a hydrocarbon toslightly reduce the water cut of the wet gas and enable the formation ofa small oil cut. For example, the hydrate inhibitor compositions cancomprise heavy aromatic naphtha to create a small oil phase therebyimproving efficacy for gas hydrate inhibition. Additionally, thesehydrate inhibitor compositions can be formulated with 2-ethyl hexanol toimprove high temperature aqueous solubility, thus, reducing fouling inmany systems.

A method for inhibiting hydrate formation in a fluid comprising waterand a gas is provided. The method comprises contacting the fluid with aneffective amount of a hydrate inhibitor composition comprising anonpolar solvent; a polar solvent; and a polymer, an oligomer, adendrimer, or an acid or salt thereof.

A hydrate inhibitor composition for use in the method can comprise, forexample, from about 5 wt. % to about 55 wt. % of heavy aromatic naphtha,from about 0.1 wt. % to about 15 wt. % of 2-ethyl hexanol, and fromabout 0.1 wt. % to about 50 wt. % of a kinetic hydrate inhibitingpolymer or a kinetic hydrate inhibiting oligomer.

An additional aspect of the invention is directed towards a method forinhibiting hydrate formation in a fluid comprising water and a gas, themethod comprising contacting the fluid with an effective amount of ahydrate inhibitor composition comprising an oil-soluble corrosioninhibitor; and a polymer, an oligomer, a dendrimer, or an acid or saltthereof.

The hydrate inhibitor composition can comprise, for example, from about5 wt. % to about 55 wt. % oil-soluble corrosion inhibitor and from about0.1 wt. % to about 55 wt. % of a kinetic hydrate inhibiting polymer or akinetic hydrate inhibiting oligomer.

The fluid comprising water and a gas can be substantially free of aliquid hydrocarbon before contacting the hydrate inhibitor composition.The fluid is substantially free of a liquid hydrocarbon when the fluidhas a concentration of liquid hydrocarbon of less than about 0.5 wt. %,0.4 wt. %, 0.3 wt. %, 0.2 wt. %, 0.1 wt. %, 0.05 wt. %, or 0.01 wt. %.

The gas can be a hydrocarbon gas. In particular, the hydrocarbon gas cancomprise methane, ethane, propane, n-butane, isobutane, isopentane, or acombination thereof.

For the methods described herein, the polymer, oligomer, or dendrimercan be a kinetic hydrate inhibiting polymer, oligomer, or dendrimer.

The polymer can be a polyvinylcaprolactone; a polyvinylpyrrolidone; acopolymer of a polyvinylcaprolactone and a polyvinylpyrrolidone; aterpolymer of a polyvinylcaprolactone, a polyvinylpyrrolidone, and apolyvinyl acetate; a dendrimeric polyesteramide derived fromhexahydrophthalic anhydride; diisopropanol amine, andN,N-bis(3-dimethylaminopropyl)amine; a substituted polyethyleneimine; apolyoxyalkylenediamine; a dicarboxylic acid-polyol polyester; apolycyclicpolyether polyol; a hyperbranched polyester polyol havinghydroxyl end groups; a hyperbranched polyester polyamine; ahyperbranched polyamidoamine; a linear polyester polyamine; or acombination thereof.

Additionally, the polymer or oligomer can comprise repeat units derivedfrom a first monomer, a second monomer, or a combination thereof.

The polymer or oligomer can comprise repeat units derived from a firstmonomer.

The first monomer can be an acrylamide monomer, acrylate monomer,N-vinyl monomer, N-vinyl caprolactam monomer, N-vinyl amine monomer,anhydride monomer, dicarboxylic acid monomer, diester monomer, diolmonomer, amine monomer, diamine monomer, dihydroxy acid monomer,dihydroxy ester monomer, hydroxy ester monomer, hydroxy acid monomer, ora combination thereof.

The acrylamide monomer can comprise N-isopropyl methacrylamide,N-isopropylacrylamide, or a combination thereof.

The polymer or oligomer can also comprise repeat units derived from asecond monomer.

The second monomer can comprise methacrylamidopropyltrimethylammoniumchloride, 2-(dimethylamino)ethyl methacrylamide,3-(acryloylamino)propyl]trimethyl ammonium chloride (APTAC),2-acryloyloxyethyltrimethyl ammonium chloride (AETAC),2-methacryloyloxyethyltrimethyl ammonium chloride (METAC),diallyldimethyl ammonium chloride (DADMAC),acryloyloxyethyldimethylbenzyl ammonium chloride (AEDBAC), ormethacryloyloxyethyldimethylbenzyl ammonium chloride (MEDBAC),2-acrylamido-2-methylpropane sulfonic acid (AMPS),2-acrylamido-2-methylpropane sulfonic acid sodium salt (AMPS sodiumsalt), or a combination thereof.

When the 2-(dimethylamino)ethyl methacrylamide is used as a secondmonomer, the resulting polymer, oligomer, or dendrimer comprising repeatunits derived therefrom can be reacted (i.e., salted) with an organicacid (e.g., acetic acid, acrylic acid, and the like) to make an acidsalt of the amine group.

The polymer or oligomer can comprise a copolymer or cooligomercomprising repeat units derived from N-isopropyl methacrylamide,methacrylamidopropyltrimethylammonium chloride, 2-(dimethylamino)ethylmethacrylamide, or a combination thereof. For example, the polymer oroligomer can comprise a copolymer or cooligomer comprising repeat unitsderived from isopropyl methacrylamide andmethacrylamidopropyltrimethylammonium chloride.

The weight average molecular weight of the polymer or oligomer can befrom about 500 Daltons to about 25,000 Daltons. Preferably, the weightaverage molecular weight of the polymer or oligomer can be from about1,000 Daltons to about 5,000 Daltons.

The nonpolar solvent can comprise an aromatic hydrocarbon solvent, analiphatic hydrocarbon solvent, a cycloaliphatic hydrocarbon, or acombination thereof. Preferably, the nonpolar solvent comprises heavyaromatic naphtha, toluene, a xylene, a hexane, diesel, kerosene, aheptane, an octane, iso-octane, or a combination thereof. Preferably,the nonpolar solvent can comprise heavy aromatic naphtha.

The polar solvent can comprise an alcohol having a molecular weight ofup to about 300 Daltons. For example, the polar solvent can comprise2-ethyl hexanol, n-butanol, t-butanol, pentanol, hexanol, octanol,decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, or acombination thereof. Preferably, the polar solvent comprises 2-ethylhexanol.

The hydrate inhibitor composition can comprise from about 5 wt. % toabout 55 wt. %, about 5 wt. % to about 50 wt. %, about 10 wt. % to about55 wt. %, or about 10 wt. % to about 50 wt. % nonpolar solvent.

The hydrate inhibitor composition can comprise from about 0.1 wt. % toabout 15 wt. %, about 0.1 wt. % to about 12 wt. %, about 0.1 wt. % toabout 10 wt. %, about 0.5 wt. % to about 15 wt. %, about 0.5 wt. % toabout 12 wt. %, about 0.5 wt. % to about 10 wt. %, about 1 wt. % toabout 15 wt. %, about 1 wt. % to about 12 wt. %, or about 1 wt. % toabout 10 wt. % polar solvent.

The hydrate inhibitor composition can comprise from about 0.1 wt. % toabout 50 wt. %, about 0.1 wt. % to about 40 wt. %, about 0.1 wt. % toabout 30 wt. %, about 5 wt. % to about 50 wt. %, or about 5 wt. % toabout 40 wt. % polymer or oligomer.

Preferably, the hydrate inhibitor composition can comprise from 10 wt. %to about 50 wt. % nonpolar solvent; from about 0.1 wt. % to about 10 wt.% polar solvent; and from about 1 wt. % to about 40 wt. % polymer oroligomer.

More preferably, the hydrate inhibitor composition can comprise fromabout 10 wt. % to about 50 wt. % of heavy aromatic naphtha; from about0.1 wt. % to about 10 wt. % of 2-ethyl hexanol; and from about 10 wt. %to about 40 wt. % of a kinetic hydrate inhibiting polymer or a kinetichydrate inhibiting oligomer.

The amount of the polymer or oligomer is based on calculating the activeamount of polymer in the composition. Thus, when using a 45-95 wt. %solution of a 20-30 wt. % active polymer solution, the amount of theactive polymer in the solution is from about 9 wt. % (i.e., 45×20/100)to about 28.5 wt. % (i.e., 95×30/100).

The oil-soluble corrosion inhibitor can comprise a substituted orunsubstituted heterocyclic compound. In particular, the substituted orunsubstituted heterocyclic compound can comprise piperidine or aderivative thereof, pyrazine or a derivative thereof, pyridazine or aderivative thereof, pyrimidine or a derivative thereof, quinolone or aderivative thereof, isoquinoline or a derivative thereof, or acombination thereof. Preferably, the substituted or unsubstitutedheterocyclic compound can comprise 3-amino-2-picoline,4-chloro-2-methoxy-pyridine, 2-(2-chloroethyl)pyridine,3-methyl-4-chloropyridine, 4-ethoxypicolinaldehyde, 2,2′-dipicolylamine,3-isocyanatopyridine, 2-amino-quinoline, 6-hydroxyquinoline,6-bromo-2-chloro-4-methylquinoline, 4-iodoquinoline, 7-bromoquinoline,or a combination thereof.

When the hydrate inhibitor composition comprises an oil-solublecorrosion inhibitor and a kinetic hydrate inhibiting polymer oroligomer, the composition can comprise from about 5 wt. % to about 75wt. %, about 5 wt. % to about 70 wt. %, about 5 wt. % to about 65 wt. %,about 5 wt. % to about 60 wt. %, about 5 wt. % to about 55 wt. %, about5 wt. % to about 50 wt. %, about 15 wt. % to about 70 wt. %, about 15wt. % to about 60 wt. %, about 15 wt. % to about 50 wt. %, about 25 wt.% to about 70 wt. %, about 25 wt. % to about 60 wt. %, about 25 wt. % toabout 50 wt. %, about 35 wt. % to about 70 wt. %, about 35 wt. % toabout 60 wt. %, or about 35 wt. % to about 50 wt. % oil-solublecorrosion inhibitor.

When the hydrate inhibitor composition comprises an oil-solublecorrosion inhibitor and a kinetic hydrate inhibiting polymer oroligomer, the composition can comprise from about 5 wt. % to about 80wt. %, about 5 wt. % to about 70 wt. %, about 5 wt. % to about 65 wt. %,about 5 wt. % to about 60 wt. %, about 5 wt. % to about 55 wt. %, about15 wt. % to about 80 wt. %, about 15 wt. % to about 70 wt. %, about 15wt. % to about 60 wt. %, about 25 wt. % to about 80 wt. %, about 25 wt.% to about 70 wt. %, about 25 wt. % to about 60 wt. %, about 35 wt. % toabout 80 wt. %, about 35 wt. % to about 70 wt. %, or about 35 wt. % toabout 60 wt. % kinetic hydrate inhibiting polymer or oligomer.

The polymer or oligomer can have a weight average molecular weight offrom about 500 Daltons to about 25,000 Daltons, from about 500 Daltonsto about 20,000 Daltons, from about 500 Daltons to about 15,000 Daltons,from about 500 Daltons to about 10,000 Daltons, from about 500 Daltonsto about 5,000 Daltons, from about 1,000 Daltons to about 25,000Daltons, from about 1,000 Daltons to about 20,000 Daltons, or from about1,000 Daltons to about 15,000 Daltons, from about 1,000 Daltons to about10,000 Daltons. Preferably, the polymer or oligomer can have a weightaverage molecular weight of from about 1,000 Daltons to about 5,000Daltons.

The hydrate inhibitor polymers can be synthesized by any means known inthe art, such as, for example radical polymerization. For example,representative polymers can be prepared by the free radicalpolymerization of a first monomer (e.g., an acrylamide monomer) and asecond monomer (e.g., a methacrylamidopropyltrimethylammonium chlorideor 2-(dimethylamino)ethyl methacrylamide monomer). Synthesis of suchpolymers is known in the art and described, for example, in U.S. Pat.No. 8,921,478.

Typically, the hydrate inhibiting polymer or oligomer can be prepared bycombining one or more vinyl monomers (e.g., monomers described as thefirst monomer and second monomer herein) in an alcohol solvent (e.g.,diethylene glycol monoethyl ether) followed by stirring and heating thereacting mixture to about 100° C. for two hours. During this time, aninitiator (e.g., t-butyl peroctanoate) is added to the reaction mixture.

The methods of the present invention involve contacting a hydrocarbonand water mixture with a suitable hydrate inhibitor composition. When aneffective amount of the hydrate inhibitor composition is used, gashydrate blockage is inhibited. In the absence of such an effectiveamount, gas hydrate blockage is not inhibited.

There are a number of factors that can be taken into account indetermining the effective amount of the hydrate inhibitor composition,including, but not necessarily limited to, the proportion of water inthe fluid, the nature of the gas (i.e., hydrocarbon gas), the nature ofthe hydrate-forming guest molecules, the temperature and pressureconditions that the mixture of gas and water are subject to, theparticular hydrate inhibitor composition employed, etc. Routineexperimentation with a particular set of conditions and/or in a specificsystem can determine the optimum dosage range to avoid the formation ofproblematic quantities of irreversible, harmful gas hydrate masses. Forexample, when considering the appropriate dose or whether additionaldoses of the hydrate inhibitor composition are needed, the temperature,pressure, brine composition, brine volume, oil composition, oil volume,and gas composition can be considered for a particular system todetermine the effective amount of the hydrate inhibitor composition toinhibit gas hydrate agglomeration under the conditions present for theparticular system to be treated.

The total time of gas hydrate inhibition will be dependent on oil fieldconditions and the number of applications. The gas hydrate formation canbe inhibited for at least 144, 150, 160, 170, 180, 190, 200, 210, 220,230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360,370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490. 500.510, 520. 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640,650, 660, 670, 680, 690, 700, 710, or 720 hours. Preferably, the gashydrate formation can be inhibited for from about 144 hours to about 480hours, about 144 hours to about 432 hours, about 144 hours to about 384hours, about 144 hours to about 336 hours, about 144 hours to about 288hours, about 144 hours to about 240 hours, or about 144 hours to about192 hours.

The hydrate inhibitor composition is added into the mixture ofhydrocarbons and water at any concentration effective to inhibit theformation of gas hydrate agglomerates under the given conditions.Accordingly, the effective amount of the compound can range from about0.1 volume percent to about 10 volume percent based on the amount ofproduced water in the well system. Preferably, the effective amount ofthe composition can range from about 0.1 volume percent to about 5volume percent. The effective amount of the composition can also rangefrom about 0.5 volume percent to about 3 volume percent. Typically, theamount of produced water is based on the amount of produced water perday that is calculated from the average volume of production per day fora particular well. The effective amount of the composition can beprovided to the system in one or more doses.

The hydrate inhibitor compositions are chemically compatible withvarious elastomers and metals. Elastomers screened for compatibility caninclude Neoprene (i.e., polychloroprene), Hypalon® (chlorosulfonatedpolyethylene synthetic rubber), nitrile butadiene rubber (NBR), ethylenepropylene rubber (EPR), Teflon® (polytetrafluoroethylene), Kalrez®(perfluoro hydrocarbon elastomer), high density polyethylene (HDPE),Nylon 11 (polyamide bioplastic), polyether ether ketone (PEEK), ethylenepropylene diene rubber (EPDM White), hydrogenated nitrile butadienerubber (HNBR), Viton® A (perfluoro hydrocarbon elastomer), Viton® B(perfluoro hydrocarbon elastomer), and Chemraz® (perfluoro hydrocarbonelastomer). Metals screened for compatibility can include AISI 1018carbon steel, Inconel® 625 nickel-chromium alloy, SS2507 stainlesssteel, copper, SS2205 stainless steel, Hastelloy C-276®(nickel-molybdenum-chromium alloy), 55304L stainless steel, and SS316Lstainless steel. The elastomers and metals are screened forcompatibility at the effective amount used in the system as describedabove. The compositions and compounds are chemically compatible withmetals when they do not cause corrosion to occur to the stainless steeland mild carbon steel components of the system and are chemicallycompatible with elastomers when they do not cause mass change orswelling.

The hydrate inhibitor compositions preferably do not interfere or reactwith any corrosion inhibitor, scale inhibitor, or other productionchemical additives that are used in the system.

Advantageously, the hydrate inhibitor compositions do not form emulsionsor foams when stored or upon use in a system. Emulsion formation cancause water quality issues in disposal of the produced water and foamingof the produced liquid can cause handling and system upset problems.

The hydrate inhibitor compositions can also reduce friction or drag whenfluids are transported. Thus, these compositions can act as dragreducers or friction reducers when added to the hydrocarbon fluids.

The methods are useful for inhibiting hydrate formation for manyhydrocarbons and hydrocarbon mixtures. The methods are particularlyuseful for lighter or low-boiling, C₁-C₅ hydrocarbon gases or gasmixtures at ambient conditions. Non-limiting example of such gasesinclude methane, ethane, propane, n-butane, isobutane, isopentane andmixtures thereof. Other examples include various natural gas mixturesthat are present in many gas and/or oil formations and natural gasliquids. The hydrates of all these low-boiling hydrocarbons are alsoreferred to as gas hydrates. The hydrocarbons may also comprise othercompounds including, but not limited to, carbon dioxide, hydrogensulfide, and other compounds commonly found in gas/oil formations orprocessing plants, either naturally occurring and/or used inrecovering/processing hydrocarbons from the formation, and mixturesthereof.

The methods can be used at any pressure that allows formation ofhydrocarbon gas hydrates. When the hydrocarbons in the mixture are lowerboiling hydrocarbons or hydrocarbon gases at ambient conditions, thepressure is usually at or greater than atmospheric pressure (i.e. about101 kPa), preferably greater than about 1 MPa, and more preferablygreater than about 5 MPa. The pressure in certain formation orprocessing units or plants could be much higher, such as greater thanabout 20 MPa. There is no specific high-pressure limit.

The temperature for contacting the mixture with the hydrate inhibitorcomposition is usually approximately at or below ambient or roomtemperature. Lower temperatures tend to favor gas hydrate formation. Atmuch higher temperatures, gas hydrates are less likely to form.

The compositions can include other means of gas hydrate inhibition, suchas thermodynamic hydrate inhibitors and anti-agglomerant hydrateinhibitors. If mixtures of gas hydrate inhibitors are used, the mixturecan be added to the hydrocarbon and water mixture through a single portor multiple ports. Alternatively, individual gas hydrate inhibitors canbe added to separate ports to access the hydrocarbon mixture.

To ensure effective inhibition of formation of gas hydrates, the hydrateinhibitor composition should be injected prior to formation of gashydrate crystals. The composition can be injected at the wellhead, atsubsea, in a riser, or a flow line. Typically, the hydrate inhibitorcomposition is injected at the wellhead or below the wellhead. Thetreatment can also be used for pipelines or anywhere in the system wherethere is a potential for gas hydrate formation.

The composition is introduced into the fluid by any means suitable forensuring dispersal of the hydrate inhibitor composition through thefluid being treated. Typically the hydrate inhibitor composition isinjected using mechanical equipment such as chemical injection pumps,piping tees, injection fittings, and the like. The compositions can bepumped into the oil/gas pipeline by using an umbilical line. Also,capillary injection systems can be used to deliver the compositions.U.S. Pat. No. 7,311,144 provides a description of an apparatus andmethods relating to capillary injection, which is herein incorporated byreference.

The contacting may be achieved in a number of ways, including mixing,blending with mechanical mixing equipment or devices, stationary mixingsetup or equipment, magnetic mixing or other suitable methods, otherequipment and means known to one skilled in the art and combinationsthereof to provide adequate contact and/or dispersion of the hydrateinhibitor composition into the mixture. The contacting can be madein-line and/or offline. The various components of the composition may bemixed prior to and/or during contact. If needed or desired, thecomposition or some of its components can be optionally removed orseparated mechanically, chemically, or by other methods known to oneskilled in the art, or by a combination of these methods after the gashydrate formation conditions are no longer present.

The hydrate inhibitor composition can further comprise one or moreadditional components, each component independently selected from thegroup consisting of a corrosion inhibitor, a solvent, an asphalteneinhibitor, a paraffin inhibitor, a scale inhibitor, an emulsifier, awater clarifier, a dispersant, a biocide, a pH modifier, a surfactant,or a combination thereof.

As described herein, a “polymer” is a macromolecule having at least 20repeat units.

As described herein, an “oligomer” is a substance having from 5-19repeat units.

As described herein, a “dendrimer” is a macromolecule having a centralcore, dendritic structures (i.e., branches), and functional surfacegroups.

Unless otherwise indicated, an “alkyl” group as described herein aloneor as part of another group is an optionally substituted linearsaturated monovalent hydrocarbon substituent containing from one tosixty carbon atoms and preferably one to thirty carbon atoms in the mainchain or eight to thirty carbon atoms in the main chain, or anoptionally substituted branched saturated monovalent hydrocarbonsubstituent containing three to sixty carbon atoms, and preferably eightto thirty carbon atoms in the main chain. Examples of unsubstitutedalkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl,i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, andthe like.

The terms “aryl” or “ar” as used herein alone or as part of anothergroup (e.g., aralkyl) denote optionally substituted homocyclic aromaticgroups, preferably monocyclic or bicyclic groups containing from 6 to 12carbons in the ring portion, such as phenyl, biphenyl, naphthyl,substituted phenyl, substituted biphenyl or substituted naphthyl. Phenyland substituted phenyl are the more preferred aryl. The term “aryl” alsoincludes heteroaryl.

The term “hydrocarbon” as used herein describes a compound orsubstituent consisting exclusively of the elements carbon and hydrogen.

The term “substituted” as in “substituted aryl,” “substituted alkyl,”and the like, means that in the group in question (i.e., the alkyl, arylor other group that follows the term), at least one hydrogen atom boundto a carbon atom is replaced with one or more substituent groups such ashydroxy (—OH), alkylthio, phosphino, amido (—CON(R_(A))(R_(B)), whereinR_(A) and R_(B) are independently hydrogen, alkyl, or aryl),amino(—N(R_(A))(R_(B)), wherein R_(A) and R_(B) are independentlyhydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl,nitro (—NO₂), an ether (—OR_(A) wherein R_(A) is alkyl or aryl), anester (—OC(O)R_(A) wherein R_(A) is alkyl or aryl), keto (—C(O)R_(A)wherein R_(A) is alkyl or aryl), heterocyclo, and the like. When theterm “substituted” introduces a list of possible substituted groups, itis intended that the term apply to every member of that group. That is,the phrase “optionally substituted alkyl or aryl” is to be interpretedas “optionally substituted alkyl or optionally substituted aryl.”

“Arylalkyl” means an aryl group attached to the parent molecule throughan alkylene group. The number of carbon atoms in the aryl group and thealkylene group is selected such that there is a total of about 6 toabout 18 carbon atoms in the arylalkyl group. A preferred arylalkylgroup is benzyl.

“Inhibiting” includes both inhibiting and preventing the formation andagglomeration of hydrate crystals.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

EXAMPLES

The following non-limiting examples are provided to further illustratethe present invention.

Example 1: Synthesis of a Kinetic Hydrate Inhibitor (KHI) Polymer

A solution of N-isopropyl methacrylamide (2.145 g, 16.866 mmol, 65polymer wt. %), a 50 wt. % active aqueous methacrylamidopropyltrimethylammonium chloride solution (0.330 g, 0.747 mmol, 5 polymer wt.%), and diethylene glycol monoethyl ether (7.535 g, 7.535 mL) werecombined, stirred, and heated to 105° C. in a capped vial which wasvented to the atmosphere with a needle. During heating, the vial cap wasremoved and t-butyl peroctanoate (0.990 g, 4.577 mmol, 30 polymer wt. %)was added. After heating for 2 hours, the vial was allowed to cool to 20to 60° C. After the vial was cooled to 20 to 60° C., 2-ethyl hexanol(0.900 g, 1.084 mL) and heavy aromatic naphtha (8.100 g, 9.000 mL) wereadded to the vial via a syringe and the vial was shaken by hand.

Example 2: Rocking Cell Tests

The rocking cell equipment consists of a rack of stainless steel cellsmounted on a central axle immersed in a temperature-controlled bath. Thebath temperature is moderated by a circulating chiller which iscontrolled by the integral computer. To rock the cells, the central axleis rotated by a computer-controlled stepper motor, which can rotate thecells up to 45° in each direction (that is, a 90° total rocking angle)at rocking rates of up to 20 times a minute. High-shear agitation of thefluids inside the cell is provided by the movement of a mixing ball(usually stainless steel although glass balls are also available) as thecells move. Each cell has a total volume of around 40 mL and will befilled with about 15 mL liquid which would give a gas:liquid ratio of˜1.7:1. Tests can also be performed to replicate the gas:liquid ratio ofthe autoclave or of the field.

Specifically, the test includes filling the cells with brine containing1,000 ppm NaCl, 500 ppm acetic acid, and 250 ppm formic acid (11.6 mL),a 1.50-1.75 volume % of a hydrate inhibitor composition, and an aminebased firm forming corrosion inhibitor (1,250 ppm). The cell was thenflushed with a synthetic test gas, described in Table 2, at atmosphericpressure to displace the air. Following flushing, the cell waspressurized with a synthetic gas to 140 bar (2,030 psi) at 24° C. Duringthe pressurization process, the pressure was monitored for anydecreases, i.e., dissolution of the gas into the liquid, and if adecrease in pressure was detected, gas was added to maintain a constantpressure of 140 bar. After a constant pressure of 140 bar was achievedin the cells, the cells were isolated from the pressure source to createan isochoric process. The bath was cooled to a temperaturerepresentative of 4.3° C. subcooling. Once the desired temperature wasachieved, the cells were rocked for 24 hours. After 24 hours, therocking was turned off and the cells were maintained in a staticposition for 72 hours. The rocking was turned on again for another 24hours. The temperature was decreased to a representative temperature of5.8° C. subcooling. Once the temperature was reached, the cells wererocked until failure, or 10 days maximum. The temperature of the cellswas increased to 24° C. The four-step testing ramp including varioussubcooling temperatures and mixing rates to mimic field conditions andis listed in Table 1.

TABLE 1 Standard KHI Performance Protocol Step Subcooling (° C.) FlowingCondition Duration (h) 1 4.3 Mixing 24 2 4.3 Static 72 3 4.3 Mixing 24 45.8 Mixing 24

The KHI performance tests were conducted with the sweet gas compositionslisted in Table 2, below.

TABLE 2 Test Gas Compositions Synthetic Test Gas Component (mol %) N₂8.47 CO₂ 11.34 Methane 78.64 Ethane 1.28 Propane 0.20 n-Butane 0.11Total 100.0

The pass/fail criteria are based on the ability of a KHI to inhibithydrate formation for 144 hours. Hydrate formation is indicated by adrop in pressure in the cell of psi. If hydrate formation occurred inthe cell prior to 144 hours, then the test was considered a fail. Theamount of time the KHI was able to inhibit hydrate formation isidentified as the hold time. A reported hold time followed by ‘+’indicates hydrates were not formed when the test was stopped. A resultof disqualification (DQ) indicates that there was a leak or a pressuretransducer malfunction in the cell.

Example 3: Hot Injection Tests

Kinetic hydrate inhibitors were tested using a hot injection test. Brinecontaining 1,000 ppm NaCl, 500 ppm acetic acid, and 250 ppm formic acid(17.5 mL) and a cross shaped stir bar were added to a 20 mL vial. Thesample was stirred at 750 rpm and heated to 60° C. An amine based filmforming corrosion inhibitor was injected at 1,250 ppm. The kinetichydrate inhibitor composition was then injected at 1.75 vol. %. Thetemperature was held at 60° C. for 10-15 minutes while checking forfouling. The vial was then cooled to 20° C. and checked again forfouling.

Example 4: Effect of Solvent on Performance of KHI

Kinetic hydrate inhibitor polymers were prepared in accordance withExample 1, above. Compositions were prepared by combining the KHIpolymer with heavy aromatic naphtha (HAN) and 2-ethyl hexanol (2-EH).The amounts of each component are listed in Table 3.

TABLE 3 Composition of KHI Polymer with HAN and 2-EH Polymer SolutionPolymer Activity solution HAN 2-EH Composition (wt. %) (wt. %) (wt. %)(wt. %) 4.1 24 100 0 0 4.2 24 80 20 0 4.3 24 80 15 5

The hydrate inhibitor compositions were subjected to the performance andhot injection tests as described in Examples 2 and 3. The results arelisted in Table 4.

TABLE 4 Results of the Hot Injection and Performance Tests Test # ofCompo- Hot Hydrate Cell cells sition inject inhibition 1 2 3 4 passing4.1 Fail Fail 123  46  83 50 0 4.2 Fail Pass  156+  156+ 145 145 4 4.3Pass Fail 146 147 DQ 135 2

The addition of HAN improved the hydrate inhibition performance. Theaddition of 2-EH led to an improvement in the hot-injection test and amodest attenuation of hydrate inhibition performance.

Example 5: Optimization of KHI Solvent Package

Kinetic hydrate inhibitor polymers were prepared in accordance withExample 1. Compositions were prepared by combining the KHI polymer withHAN and 2-EH and are listed in Table 5. In these compositions, the wt. %of 2-EH was held constant while the wt. % of the HAN was varied.

TABLE 5 Composition of Polymer and Solvent Package Polymer SolutionPolymer Activity solution HAN 2-EH Composition (wt. %) (wt. %) (wt. %)(wt. %) 5.1 24 65 30 5 5.2 24 71.25 23.75 5 5.3 24 77.50 17.5 5 5.4 2483.75 11.25 5 5.5 24 90 5 5

The hydrate inhibitor compositions were subjected to the performance andhot injection tests as described in Examples 2 and 3. The results arelisted in Table 6.

TABLE 6 Results of the Hot Injection and Performance Tests Hot Hydrate #of cells Composition inject inhibition Cell 1 Cell 2 passing 5.1 PassPass 150 148 2 5.2 Pass Fail 130 — 0 5.3 Pass Fail 124 DQ 0 5.4 PassFail 125 — 0 5.5 Pass Fail 126 124 0

Only composition 5.1 provided optimal performance in both the hotinjection and hydrate inhibition tests. These results indicate thatincreased HAN concentration leads to improved performance.

Example 6: Optimization of 2-EH Concentration

Kinetic hydrate inhibitor polymers were prepared in accordance withExample 1. Compositions were prepared by combining the KHI polymer withHAN and 2-EH and are listed in Table 7. The wt. % of 2-ethyl hexanol wasadjusted as compared to the compositions described in Example 5.

TABLE 7 Compositions of Polymer and Solvent Package Polymer SolutionPolymer Activity solution HAN 2-EH Composition (wt. %) (wt. %) (wt. %)(wt. %) 6.1 24 65 35 0 6.2 24 65 34 1 6.3 24 65 33 2 6.4 24 65 32 3 6.524 65 31 4 6.6 24 65 30 5

The hydrate inhibitor compositions were subjected to the performance andhot injection tests as described in Examples 2 and 3. The results arelisted in Table 8.

TABLE 8 Results of the Hot Injection and Performance Tests CompositionHot injection 6.1 Fail 6.2 Fail 6.3 Borderline 6.4 Pass 6.5 Pass 6.6Pass

Reducing the wt. % of 2-EH lower than 3 wt. %, negatively affected theperformance in the hot injection test.

Example 7: Effects of Increased Polymer Activity in Polymerization Step

Kinetic hydrate inhibitor polymers were prepared in accordance withExample 1. Compositions were prepared by combining the KHI polymer withHAN and 2-EH and are listed in Table 9. The wt. % of HAN and 2-EH wereheld constant while the wt. % activity of the polymer was varied.

TABLE 9 Formulations of Polymer and Solvent Package Polymer SolutionPolymer Activity solution HAN 2-EH Formulation (wt. %) (wt. %) (wt. %)(wt. %) 7.1 24 65 32 3 7.2 27 65 32 3 7.3 30 65 32 3

The hydrate inhibitor compositions were subjected to the performance andhot injection tests as described in Examples 2 and 3. The results arelisted in Table 10.

TABLE 10 Results of the Hot Injection and Performance Tests Number HotHydrate Average inject inhibition # of cells Composition MW Test TestCell 1 Cell 2 Cell 3 Cell 4 passing 7.1 1,329 Pass Fail 143 140 134 15 07.2 1,251 Pass Fail 138 138 138 138 0 7.3 1,259 Pass Fail 138 143 138139 0

The increased polymer activity did not lead to a significant boost inperformance, nor did it significantly affect polymer molecular weight.

Example 8: Further Optimization of KHI Solvent Package

Kinetic hydrate inhibitor polymers were prepared in accordance withExample 1. Compositions were prepared by combining the KHI polymer withHAN and 2-EH and are listed in Table 11. The wt. % activity of thepolymer was held constant while the wt. % of the polymer solution, heavyaromatic naphtha, and 2-ethyl hexanol were varied.

TABLE 11 Compositions of Polymer and Solvent Package Polymer Activitysolution HAN 2-EH Composition (wt. %) (wt. %) (wt. %) (wt. %) 8.1 30 6036 4 8.2 30 55 40.5 4.5 8.3 30 50 45 5

The hydrate inhibitor compositions were subjected to the performance andhot injection tests as described in Examples 2 and 3. The results arelisted in Table 12.

TABLE 12 Results of the Hot Injection and Performance Tests Hot Hydrate# of Compo- inject inhibition Cell Cell Cell Cell cells sition Test Test1 2 3 4 passing 8.1 Pass Pass 161+ 161+ 161+ 161+ 4 8.2 Pass Pass 161+161+ 161+ 161+ 4 8.3 Pass Pass DQ 161+ 161+ DQ 2

Compositions with at least 40% solvent package passed the hydrateinhibition test.

Example 9: Reduction of Hydrate Inhibitor Composition Dose Rate to 1.50%

Kinetic hydrate inhibitor polymers were prepared in accordance withExample 1. Compositions were prepared by combining the KHI polymer withHAN and 2-EH and are listed in Table 13. The wt. % activity of thepolymer was held constant while the wt. % of the polymer solution, HAN,and 2-EH were varied.

TABLE 13 Compositions of Polymer and Solvent Package Polymer Activitysolution HAN 2-EH Composition (wt. %) (wt. %) (wt. %) (wt. %) 9.1 30 5540.5 4.5

The hydrate inhibitor compositions were subjected to the performance andhot injection tests as described in Examples 2 and 3, except the doserate was decreased to 1.50 vol %. The results are listed in Table 14.

TABLE 14 Results of the Hot Injection and Performance Tests Test # ofHot Hydrate Cell cells Composition inject inhibition 1 2 3 4 passing 9.1Pass Pass 157 170 165 164 4

Compositions with at least 40% solvent package passed the hydrateinhibition test and the hot injection test at a reduced dose rate of1.50 vol %.

Example 10: Visual Rocking Cell Test

The visual rocking cell equipment consists of rack of high pressurecells made from sapphire tubes. Each tube contains a stainless steelball for mixing the fluids. To rock the tubes, the rack is moved up anddown using a computer-controlled stepper motor. Each cell has a totalvolume of around 20 mL and will be filled with 10 mL liquid and thencharged with a synthetic gas composition to the desired pressure. Therack containing the cells can be immersed in a temperature controlledwater bath.

Specifically, the test includes filling the tubes with approximately 10mL DI water, a 1.10-2.00 volume % of a hydrate inhibitor composition,and an alkyl pyridine or quinolone based corrosion inhibitor (45 wt. %),or HAN (45 wt. %). The tubes were then flushed with a synthetic gascomposition, described in Table 15, at atmospheric pressure to displacethe air. Following flushing, the cells were pressurized to 172 bar(2,500 psi) at 29° C. During the pressurization process, the pressurewas monitored for any decreases, i.e., dissolution of the gas into theliquid, and if a decrease in pressure was detected, gas was added tomaintain a constant pressure of 172 bar. After a constant pressure of172 bar was achieved in the cells, the cells were isolated from thepressure source to create an isochoric process. The bath was cooled from29° C. to 8.8° C. over the course of two hours. The tubes were rockedduring the cooling process. The tubes were rocked at 8.8° C. until theend of the test.

TABLE 15 Synthetic Gas Composition Parameter mole % Nitrogen 0.39Methane 87.26 Ethane 7.57 Propane 3.10 iso-Butane 0.49 n-Butane 0.79iso-Pentane 0.20 n-Pentane 0.20

Hydrate formation is indicated by a drop in pressure in the cell of psi.The amount of time the KHI was able to inhibit hydrate formation isidentified as the hold time. A reported hold time followed by ‘+’indicates hydrates were not formed when the test was stopped.

Example 11: Effect of Corrosion Inhibitor on Performance of KHI

Kinetic hydrate inhibitor polymers were prepared in accordance withExample 1. Compositions were prepared by combining the KHI polymer withtwo corrosion inhibitors, an alkyl pyridine and a quinolone, and arelisted in Table 16.

TABLE 16 Compositions of Polymer and Corrosion Inhibitor Dose RatePolymer Alkyl (vol % of solution HAN Pyridine Quinoline Compositionwater) (wt.%) (wt.%) (wt.%) (wt.%) 11.1 1.10 100 — — — 11.2 1.10 100 — —— 11.3 2.00 55 45 — — 11.4 2.00 55 45 — — 11.5 2.00 55 — 45 — 11.6 2.0055 — 45 — 11.7 2.00 55 — — 45 11.8 2.00 55 — — 45

The hydrate inhibitor compositions were subjected to the performancetest as described in Example 10. The results are listed in Table 17.

TABLE 17 Results of the Performance Test Hydrate Inhibition Composition(hrs) 11.1 16   11.2 20   11.3 56+ 11.4 56+ 11.5 56+ 11.6 56+ 11.7 56+11.8 56+

The addition of a corrosion inhibitor or HAN provided a significantperformance increase to the KHI alone.

When introducing elements of the present invention or the preferredembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

In view of the above, it will be seen that the several objects of theinvention are achieved and other advantageous results attained.

As various changes could be made in the above products and methodswithout departing from the scope of the invention, it is intended thatall matter contained in the above description shall be interpreted asillustrative and not in a limiting sense.

What is claimed is: 1-25. (canceled)
 26. A method for inhibiting hydrateformation in a fluid comprising water and a gas, the method comprisingcontacting the fluid with an effective amount of a hydrate inhibitorcomposition comprising an oil-soluble corrosion inhibitor and a polymer,an oligomer, a dendrimer, or an acid or salt thereof.
 27. The method ofclaim 26, wherein the polymer, oligomer, or dendrimer is a kinetichydrate inhibiting polymer, oligomer, or dendrimer.
 28. The method ofclaim 26 or 27, wherein the fluid is substantially free of a liquidhydrocarbon before contacting the hydrate inhibitor composition.
 29. Themethod of claim 26, wherein the polymer or oligomer comprises repeatunits derived from a first monomer, a second monomer, or a combinationthereof.
 30. The method of claim 29, wherein the polymer or oligomercomprises repeat units derived from a first monomer and a secondmonomer.
 31. The method of claim 29, wherein the first monomer comprisesan acrylamide monomer, acrylate monomer, N-vinyl amide monomer, N-vinylcaprolactam monomer, N-vinyl amine monomer, anhydride monomer,dicarboxylic acid monomer, diester monomer, diol monomer, amine monomer,diamine monomer, dihydroxy acid monomer, dihydroxy ester monomer,hydroxy ester monomer, hydroxy acid monomer, or a combination thereof.32. The method of claim 31, wherein the first monomer comprisesN-isopropyl methacrylamide, N-isopropylacrylamide, or a combinationthereof.
 33. The method of claim 29, wherein the second monomercomprises methacrylamidopropyltrimethylammonium chloride (MAPTAC),2-(dimethylamino)ethyl methacrylamide, 3-(acryloylamino)propyl]trimethylammonium chloride (APTAC), 2-acryloyloxyethyltrimethyl ammonium chloride(AETAC), 2-methacryloyloxyethyltrimethyl ammonium chloride (METAC),diallyldimethyl ammonium chloride (DADMAC),acryloyloxyethyldimethylbenzyl ammonium chloride (AEDBAC), ormethacryloyloxyethyldimethylbenzyl ammonium chloride (MEDBAC), or acombination thereof.
 34. The method of claim 26, wherein the polymer oroligomer is a copolymer or cooligomer comprising repeat units derivedfrom N-isopropyl methacrylamide, methacrylamidopropyltrimethylammoniumchloride, 2-(dimethylamino)ethyl methacrylamide, or a combinationthereof.
 35. The method of claim 34, wherein the polymer or oligomer isa copolymer or cooligomer comprising repeat units derived from isopropylmethacrylamide and methacrylamidopropyltrimethylammonium chloride. 36.The method of claim 26, wherein the weight average molecular weight ofthe polymer is from about 500 Daltons to about 25,000 Daltons.
 37. Themethod of claim 26, wherein the oil-soluble corrosion inhibitorcomprises a substituted or unsubstituted heterocyclic compound.
 38. Themethod of claim 37, wherein the oil-soluble corrosion inhibitorcomprises piperidine or a derivative thereof, pyrazine or a derivativethereof, pyridazine or a derivative thereof, pyrimidine or a derivativethereof, quinolone or a derivative thereof, isoquinoline or a derivativethereof, or a combination thereof.
 39. The method of claim 37, whereinthe substituted or unsubstituted heterocyclic compound can comprise3-amino-2-picoline, 4-chloro-2-methoxy-pyridine,2-(2-chloroethyl)pyridine, 3-methyl-4-chloropyridine,4-ethoxypicolinaldehyde, 2,2′-dipicolylamine, 3-isocyanatopyridine,2-amino-quinoline, 6-hydroxyquinoline,6-bromo-2-chloro-4-methylquinoline, 4-iodoquinoline, 7-bromoquinoline,or a combination thereof.
 40. The method of claim 26, wherein thehydrate inhibitor composition comprises from about 5 wt. % to about 55wt. % oil-soluble corrosion inhibitor and from about 0.1 wt. % to about55 wt. % polymer or oligomer.
 41. The method of claim 40, wherein thehydrate inhibitor composition comprises from about 10 wt. % to about 50wt. % oil-soluble corrosion inhibitor and from about 1 wt. % to about 40wt. % polymer or oligomer.
 42. A method for inhibiting hydrate formationin a fluid comprising water and a gas, the method comprising contactingthe fluid with an effective amount of a hydrate inhibitor compositioncomprising from about 5 wt. % to about 55 wt. % of alkyl pyridine andfrom about 0.1 wt. % to about 55 wt. % of a kinetic hydrate inhibitingpolymer.
 43. A method for inhibiting hydrate formation in a fluidcomprising water and a gas, the method comprising contacting the fluidwith an effective amount of a hydrate inhibitor composition comprisingfrom about 5 wt. % to about 55 wt. % of quinoline and from about 0.1 wt.% to about 55 wt. % of a kinetic hydrate inhibiting polymer.
 44. Themethod of claim 42, wherein the hydrate inhibitor composition comprisesfrom about 10 wt. % to about 50 wt. % of the alkyl pyridine and fromabout 1 wt. % to about 40 wt. % of the kinetic hydrate inhibitingpolymer.
 45. The method of claim 42, wherein the hydrate inhibitorcomposition comprises from about 10 wt. % to about 50 wt. % of thequinoline and from about 1 wt. % to about 40 wt. % of the kinetichydrate inhibiting polymer.